We introduce a new reagent class, 2-azatrienes, as a platform for catalytic enantioselective synthesis of allylic amines. Herein, we demonstrate their promise by diasteredivergent and enantioselective synthesis of <i>syn</i>- and <i>anti</i>-1,2-diamines by Cu-bis(phosphine)-catalyzed reductive couplings with imines. With Ph-BPE, <i>anti</i>-diamines are obtained, and with the rarely utilized t-Bu-BDPP, <i>syn</i>-diamines are generated.<br />